Oxyethylene copolymers with chloromethyl and (alkylthio)methyl or (alkylsulfonyl)methyl side groups: Syntheses and Tg/composition relationships

New classes of copolymers, poly[oxy(chloromethyl)ethylene]/poly[oxy-((alkylthio)methyl)ethylene] copolymers (CE-ATEs), poly[oxy((alkylthio)methyl)-ethylene]s (ATEs), poly[oxy(chloromethyl)ethylene]/poly[oxy((alkylsulfonyl)meth-yl)ethylene] copolymers (CE-ASEs), and poly[oxy((alkylsulfonyl)methyl)ethylene]s (ASEs) have been made for the first time. The thioether-containing polymers (CE-ATEs and ATEs) were synthesized by reacting poly[oxy(chloromethyl)ethylene] (CE, poly(epichlorohydrin)) with different amounts of sodium alkanethiolates. The sulfone-containing polymers (CE-ASEs and ASEs) were synthesized by oxidizing the CE-ATEs and ATEs using m-chloroperoxybenzoic acid. The Fox equation, a linear relationship, fit the T_g/composition data for most CE-ATEs. The T_g's of the CE-ASEs showed positive deviations from those calculated using the Fox equation. The Johnston equation, in which steric and/or polar interactions between dissimilar monomeric units are considered by using T_gAB (the T_g of the AB or BA dyad), fit the T_g/composition data for all copolymers in this study. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 495–504, 1998     

Grammatical Gender Disambiguates Syntactically Similar Nouns

Recent research into grammatical gender from the perspective of information theory has shown how seemingly arbitrary gender systems can ease processing demands by guiding lexical prediction. When the gender of a noun is revealed in a preceding element, the list of possible candidates is reduced to the nouns assigned to that gender. This strategy can be particularly effective if it eliminates words that are likely to compete for activation against the intended word. We propose syntax as the crucial context within which words must be disambiguated, hypothesizing that syntactically similar words should be less likely to share a gender cross-linguistically. We draw on recent work on syntactic information in the lexicon to define the syntactic distribution of a word as a probability vector of its participation in various dependency relations, and we extract such relations for 32 languages from the Universal Dependencies Treebanks. Correlational and mixed-effects regression analyses reveal that syntactically similar nouns are less likely to share a gender, the opposite pattern that is found for semantically and orthographically similar words. We interpret this finding as a design feature of language, and this study adds to a growing body of research attesting to the ways in which functional pressures on learning, memory, production, and perception shape the lexicon in different ways.     

The value of foresight

Suppose you have one unit of stock, currently worth 1, which you must sell before time $T$. The Optional Sampling Theorem tells us that whatever stopping time we choose to sell, the expected discounted value we get when we sell will be 1. Suppose however that we are able to see $a$ units of time into the future, and base our stopping rule on that; we should be able to do better than expected value 1. But how much better can we do? And how would we exploit the additional information? The optimal solution to this problem will never be found, but in this paper we establish remarkably close bounds on the value of the problem, and we derive a fairly simple exercise rule that manages to extract most of the value of foresight.     

The (3+1)-dimensional Monge-Ampère equation in discontinuity wave theory: Application of a reciprocal transformation

It is shown that the complete exceptionality condition for discontinuity waves associated with a second-order non-linear hyperbolic equation of the form

Dual emission laser induced fluorescence for direct planar scalar behavior measurements

 In this paper, a new method of measuring scalar behavior in bulk aqueous fluid flows is presented. Using a simple ratiometric scheme, laser induced fluorescence from organic dyes can be normalized so that direct measurements of a scalar in the flow are possible. The technique dual emission laser induced fluorescence (DELIF) relies on normalizing the fluorescence emission intensity of one dye with the fluorescence emission intensity of a second dye. Since each dye fluoresces at a different wavelength, one can optically separate the emission of each dye. This paper contains an overview of the basic ratiometric technique for pH and temperature measurements as well as the spectral properties of nine water soluble dyes. It also covers the three most significant sources of error in DELIF applications. To demonstrate the technique, steady state turbulent jet mixing and temperature fields in a thermal plume were quantified. The accuracy was camera limited at under 3% of the fluorescence ratio which corresponds to 0.1 pH units or 1.8 °C. Received 7 June 1996/Accepted 17 June 1997     

Benzene Solubility in Ionic Liquids: Working Toward an Understanding of Liquid Clathrate Formation

The solubility of benzene in 15 imidazolium, pyrrolidinium, pyridinium, and piperidinium ionic liquids has been determined; the resulting, benzene‐saturated ionic liquid solutions, also known as liquid clathrates, were examined with ¹H and ¹⁹F nuclear magnetic resonance spectroscopy to try and understand the molecular interactions that control liquid clathrate formation. The results suggest that benzene interacts primarily with the cation of the ionic liquid, and that liquid clathrate formation (and benzene solubility) is controlled by the strength of the cation–anion interactions, that is, the stronger the cation–anion interaction, the lower the benzene solubility. Other factors that were determined to be important in the final amount of benzene in any given liquid clathrate phase included attractive interactions between the anion and benzene (when significant), and larger steric or free volume demands of the ions, both of which lead to greater benzene solubility.     

Profiling of the secretome of human cancer cells: Preparation of supernatant for proteomic analysis

Secretomic analysis requires removal of serum proteins from cell‐culture media. We evaluate the proteins washed from cells prepared in bovine serum‐supplemented medium. PBS and serum‐free‐medium (SFM) were the washing solutions. A Bradford assay was used for total protein concentration and a 1D gel and LC‐MS/MS, to assign the protein to human or bovine origin. For both wash solutions, all bovine protein had been removed by the third wash, without compromising the number of living cells. Further washes reduced the number of living cells, especially when using PBS. Proteomic analysis of wash supernatant showed that SFM induced greater lysis of dead cells. Three washes were sufficient to minimize the effects on cell viability, while still removing serum proteins. Washing in SFM resulted in contamination of the wash supernatant with lysed dead cell proteins. Washed cells were incubated in SFM and exposed to ionizing radiation. Analysis of the supernatant showed an increase in human cytoplasmic, plasma membrane, and nuclear protein following irradiation. Secreted proteins were also detected, but in smaller quantities. The significance of these findings extend to in vitro studies of bystander phenomena, since the proteins of lysed dead cells may participate in driving bystander responses.     

Ionic Fluids Containing Both Strongly and Weakly Interacting Ions of the Same Charge Have Unique Ionic and Chemical Environments as a Function of Ion Concentration

Liquid multi‐ion systems made by combining two or more salts can exhibit charge ordering and interactions not found in the parent salts, leading to new sets of properties. This is investigated herein by examining a liquid comprised of a single cation, 1‐ethyl‐3‐methylimidazolium ([C₂mim]⁺), and two anions with different properties, acetate ([OAc]^?) and bis(trifluoromethylsulfonyl)imide ([NTf₂]^?). NMR and IR spectroscopy indicate that the electrostatic interactions are quite different from those in either [C₂mim][OAc] or [C₂mim][NTf₂]. This is attributed to the ability of [OAc]^? to form complexes with the [C₂mim]⁺ ions at greater than 1:1 stoichiometries by drawing [C₂mim]⁺ ions away from the less basic [NTf₂]^? ions. Solubility studies with molecular solvents (ethyl acetate, water) and pharmaceuticals (ibuprofen, diphenhydramine) show nonlinear trends as a function of ion content, which suggests that solubility can be tuned through changes in the ionic compositions.     

Pd-η 3-C6H9 complexes of the Trost modular ligand: high nuclearity columnar aggregation controlled by concentration,solvent and counterion

Under optimised conditions, the Trost modular ligand (TML) series induces high levels of asymmetric induction in an extraordinarily wide range of reactions involving palladium π-allyl intermediates. Prior mechanistic investigations into reactions involving Pd-η ³-C₆H₉ intermediates have focussed on the monomeric 13-membered ring formed via P,P-chelation of the ligand to Pd. However, it is also recognised that ring-opening oligomerisation provides a pool of high nuclearity Pd-η ³-C₆H₉ species that, by affording a low level, or even the opposite sense, of asymmetric induction relative to the mononuclear species, are responsible for a reduction in selectivity under non-optimised conditions. Herein we describe an investigation by NMR spectroscopy, molecular mechanics, molecular dynamics, and small-angle neutron scattering (SANS), of a Pd-η ³-C₆H₉ cation bearing the 1,2-diaminocyclohexane TML ligand (2). Using both nondeuterated and perdeuterated (D₄₇) isotopologues of the resulting complexes ([1]⁺), we show that a two-stage oligomerisation-aggregation process forms self assembled cylindrical aggregates of very high nuclearity (up to 56 Pd centres). We also investigate how concentration, solvent and counter-anion all modulate the extent of oligomerisation.     

Visualization of steady streaming near oscillating spheroids

Experimental studies of steady streaming flows are presented for spheroids of various aspect ratios oscillating in a viscous fluid along their axis of symmetry at Reynolds numbers up to 150 and normalized oscillation amplitudes up to 1.2. The steady streaming component of the flow is visualized using phase-locked particle pathline images along the central plane of the spheroid. The extent of the inner region of the flow, characterized by the distance to the stagnation points, appears to depend on a length scale based on the spheroid aspect ratio and equivalent radius. Spheroids were also oscillated at a nonzero angle with respect to their axis of symmetry. The angular displacement of the stagnation points on the surface of these obliquely oscillated spheroids is related to the aspect ratio and the angle of oscillation.